Light-emitting diodes (LEDs) based on perovskite semiconductor materials with tunable emission wavelength in visible light range as well as narrow linewidth are potential competitors among current light-emitting display technologies, but still suffer from severe instability driven by electric field. Here, we develop a stable, efficient and high-color purity hybrid LED with a tandem structure by combining the perovskite LED and the commercial organic LED technologies to accelerate the practical application of perovskites. Perovskite LED and organic LED with close photoluminescence peak are selected to maximize photon emission without photon reabsorption and to achieve the narrowed emission spectra. By designing an efficient interconnecting layer with p-type interface doping that provides good opto-electric coupling and reduces Joule heating, the resulting green emitting hybrid LED shows a narrow linewidth of around 30 nm, a peak luminance of over 176,000 cd m-2, a maximum external quantum efficiency of over 40%, and an operational half-lifetime of over 42,000 h.
Mixed Br/Cl perovskite nanocrystals (PeNCs) exhibit bright pure-blue emission benefiting for fulfilling the Rec. 2100 standard. However, phase segregation remains a significant challenge that severely affects the stability and emission spectrum of perovskite light-emitting diodes (PeLEDs). Here, we demonstrate the optimization of the spacing between polydentate functional groups of polymer ligands to match the surface pattern of CsPbBr1.8Cl1.2 PeNCs, resulting in effective synergistic passivation effect and significant improvements in PeLED performances. The block and alternating copolymers with different inter-functional group spacing are facilely synthesized as ligands for PeNCs. Surprisingly, block copolymers with a higher functional group density do not match PeNCs, while alternating copolymers enable efficient PeNCs with the high photoluminescence intensity, low non-radiative recombination rate and high exciton binding energy. Density functional theory calculations clearly confirm the almost perfect match between alternating copolymers and PeNCs. Finally, pure-blue PeLEDs are achieved with the emission at 467 nm and Commission Internationale de l'Eclairage (CIE) coordinates of (0.131, 0.071), high external quantum efficiency (9.1%) and record spectral and operational stabilities (~ 80 mins) in mixed-halide PeLEDs. Overall, this study contributes to designing the polymer ligands and promoting the development of high-performance and stable pure-color PeLEDs towards display applications.
Dielectric constant of non-fullerene acceptors plays a critical role in organic solar cells in terms of exciton dissociation and charge recombination. Current acceptors feature a dielectric constant of 3-4, correlating to relatively high recombination loss. We demonstrate that selenium substitution on acceptor central core can effectively modify molecule dielectric constant. The corresponding blend film presents faster hole-transfer of ~5 ps compared to the sulfur-based derivative (~10 ps). However, the blends with Se-acceptor also show faster charge recombination after 100 ps upon optical pumping, which is explained by the relatively disordered stacking of the Se-acceptor. Encouragingly, dispersing the Se-acceptor in an optimized organic solar cell system can interrupt the disordered aggregation while still retain high dielectric constant. With the improved dielectric constant and optimized fibril morphology, the ternary device exhibits an obvious reduction of non-radiative recombination to 0.221 eV and high efficiency of 19.0%. This work unveils heteroatom-substitution induced dielectric constant improvement, and the associated exciton dynamics and morphology manipulation, which finally contributes to better material/device design and improved device performance.
For stable operation of ultrathin flexible transparent electrodes (uFTEs), it is critical to implement effective risk management during concurrent multi-loading operation of electrical bias and mechanical folding cycles in high-humidity environments. Despite extensive efforts in preparing solution-processed uFTEs with cost-effective and high-throughput means, achieving in-situ nano-adhesion in heterogeneous metal-oxide nanocomposites remains challenging. In this work, we observed by serendipity liquid-like behaviour of transparent metal-oxide-semiconductor zinc oxide nanoparticles (ZnONPs) onto silver nanowires (AgNWs) developed by in-situ solution processed method (iSPM). This enabled us to address the long-standing issue of vulnerability in the nanocomposite caused by the interface of dissimilar materials between AgNWs and ZnONPs, resulting in a remarkably improved multi-loading operation. Importantly, substrate-integrated uFTEs constituted of the metal-oxide nanocomposite electrode semi-embedded in the polymer matrix of greatly thin <0.5 µm thickness is successfully demonstrated with the smooth surface topography, promoted by the tri-system integration including (i) AgNW-AgNW, (ii) ZnONP-ZnONP, and (iii) AgNW-ZnONP systems. Our finding unveils the complex interfacial dynamics associated with the heterogeneous interface system between AgNWs and ZnONPs and holds great promise in understanding the in-situ nano-adhesion process and increasing the design flexibility of next generation solution-processed uFTEs.
Chiral-induced spin selectivity (CISS) effect provides innovative approach to spintronics and quantum-based devices for chiral materials. Different from the conventional ferromagnetic devices, the application of CISS effect is potential to operate under room temperature and zero applied magnetic field. Low dimensional chiral perovskites by introducing chiral amines are beginning to show significant CISS effect for spin injection, but research on chiral perovskites is still in its infancy, especially on spin-light emitting diode (spin-LED) construction. Here, the spin-QLEDs enabled by 2D chiral perovskites as CISS layer for spin-dependent carrier injection and CdSe/ZnS quantum dots (QDs) as light emitting layer are reported. The regulation pattern of the chirality and thickness of chiral perovskites, which affects the circularly polarized electroluminescence (CP-EL) emission of spin-QLED, is discovered. Notably, the spin injection polarization of 2D chiral perovskites is higher than 80% and the CP-EL asymmetric factor (gCP-EL ) achieves up to 1.6 × 10-2 . Consequently, this work opens up a new and effective approach for high-performance spin-LEDs.
Nickel oxide (NiOx ) is one of the most promising hole transport materials for inverted perovskite solar cells (PSCs). However, its application is severely restrained due to unfavorable interfacial reactions and insufficient charge carrier extraction. Herein, a multifunctional modification at the NiOx /perovskite interface is developed via introducing fluorinated ammonium salt ligand to synthetically solve the obstacles. Specifically, the interface modification can chemically convert detrimental Ni≥3+ to lower oxidation state, resulting in the elimination of interfacial redox reactions. Meanwhile, interfacial dipole is incorporated simultaneously to tune the work function of NiOx and optimize energy level alignment, which effectively promotes the charge carrier extraction. Therefore, the modified NiOx -based inverted PSCs achieve a remarkable power conversion efficiency (PCE) of 22.93%. Moreover, the unencapsulated devices obtain a significantly enhanced long-term stability, maintaining over 85% and 80% of the initial PCEs after storage in ambient air with a high relative humidity of 50-60% for 1000 h and continuous operation at maximum power point under one-sun illumination for 700 h, respectively.
Advancing inverted (p-i-n) perovskite solar cells (PSCs) is critical for commercial applications given their compatibility with different bottom cells for tandem photovoltaics, low-temperature processability (≤100 °C), and promising operational stability. Although inverted PSCs have achieved an efficiency of over 25 % using doped or expensive organic hole transport materials (HTMs), their synthesis cost and stability still cannot meet the requirements for their commercialization. Recently, dopant-free and low-cost non-stoichiometric nickel oxide nanocrystals (NiOx NCs) have been extensively studied as a low-cost and effective HTM in perovskite optoelectronics. In this minireview, we summarize the synthesis and surface-functionalization methods of NiOx NCs. Then, the applications of NiOx NCs in other perovskite optoelectronics beyond photovoltaics are discussed. Finally, we provide a perspective for the future development of NiOx NCs for the commercialization of perovskite optoelectronics.
Materials with circularly polarized luminescence (CPL) activity are promising in many chiroptoelectronics fields, such as for biological probes, asymmetric photosynthesis, information storage, spintronic devices, and so on. Promoting the value of the dissymmetry factor (glum) for the CPL-active materials based on chiral perovskite draws increasing attention since a higher glum value indicates better CPL. In this work, we find that, after being treated with a facile solvent modulation strategy, the chirality of 2D chiral perovskite films has been enhanced a lot, which we attribute to an increased lattice distortion degree. By forming chiral perovskite/quantum dot (QD) composites, the CPL-active material is successfully obtained. The calculated maximum |glum| of these composites increased over 4 times after solvent modulation treatment (1.53 × 10-3 for the pristine sample of R-DMF and 6.91 × 10-3 for R-NMP) at room temperature. Moreover, the enhancement of the CPL intensity is ascribed to two aspects: one is the generation and transportation of spin-polarized charge carriers from chiral perovskite films to combine in the QD layer, and the other is the solvent modulation strategy to enlarge the lattice distortion of chiral perovskite films. This facile route provides an effective way to construct CPL-active materials. More importantly, this kind of composite material (chiral perovskite film/QD layer) can be easily applied for fabricating circularly polarized light-emitting diode devices for electroluminescence.
Among the emerging photovoltaic technologies, rigid perovskite solar cells (PSCs) have made tremendous development owing to their exceptional power conversion efficiency (PCE) of up to 25.7%. However, the record PCE of flexible PSCs (≈22.4%) still lags far behind their rigid counterparts and their mechanical stabilities are also not satisfactory. Herein, through modifying the interface between perovskite and hole transport layer via pentylammonium acetate (PenAAc) molecule a highly efficient and stable flexible inverted PSC is reported. Through synthetic manipulation of anion and cation, it is shown that the PenA+ and Ac- have strong chemical binding with both acceptor and donor defects of surface-terminating ends on perovskite films. The PenAAc-modified flexible PSCs achieve a record PCE of 23.68% (0.08 cm2 , certified: 23.35%) with a high open-circuit voltage (VOC ) of 1.17 V. Large-area devices (1.0 cm2 ) also realized an exceptional PCE of 21.52%. Moreover, the fabricated devices show excellent stability under mechanical bending, with PCE remaining above 91% of the original PCE even after 5000 bends.
The inorganic hole transport layer of nickel oxide (NiOx ) has shown highly efficient, low-cost, and scalable in perovskite photovoltaics. However, redox reactions at the interface between NiOx and perovskites limit their commercialization. In this study, ABABr (4-(2-Aminoethyl) benzoic acid bromide) between the NiOx and different perovskite layers to address the issues has been introduced. How the ABABr interacts with NiOx and perovskites is experimentally and theoretically investigated. These results show that the ABABr molecule chemically reacts with the NiOx via electrostatic attraction on one side, whereas on the other side, it forms a strong hydrogen bond via the NH3 + group with perovskites layers, thus directly diminishing the redox reaction between the NiOx and perovskites layers and passivating the layer surfaces. Additionally, the ABABr interface modification leads to significant improvements in perovskite film morphology, crystallization, and band alignment. The perovskites solar cells (PSCs) based on an ABABr interface modification show power conversion efficiency (PCE) improvement by over 13% and maintain over 90% of its PCE after continuous operation at maximum power point for over 500 h. The work not only contributes to the development of novel interlayers for stable PSCs but also to the understanding of how to prevent interface redox reactions.
Perovskite solar cells (PVSCs) have drawn great attention due to their high processability and superior photovoltaic properties. However, their further development is often hindered by severe nonradiative recombination at interfaces that decreases power conversion efficiency (PCE). To this end, a facile strategy to construct a 3D/2D vertical heterostructure to reduce the energy loss in PVSCs is developed. The heterostructure is contrived through the van der Waals integration of 2D perovskite ((BA)4 AgBiBr8 ) nanosheets onto the surface of 3D-FAPbI3 -based perovskites. The large bandgap of (BA)4 AgBiBr8 enables the formation of type-I heterojunction with 3D-FAPbI3 -based perovskites, which serves as a barrier to suppress the trap-assisted recombination at the interface. As a result, a satisfying PCE of 24.48% is achieved with an improved open-circuit voltage (VOC ) from 1.13 to 1.17 V. Moreover, the 2D perovskite nanosheets can effectively mitigate the iodide ion diffusion from perovskite to the metal electrode, hence enhancing the device stability. 3D/2D architectured devices retain ≈90% of their initial PCE under continuous illumination or heating after 1000 h, which are superior to 3D-based devices. This work provides an effective and controllable strategy to construct 3D/2D vertical heterostructure to simultaneously boost the efficiency and stability of PVSCs.
The development of in situ growth methods for the fabrication of high-quality perovskite single-crystal thin films (SCTFs) directly on hole-transport layers (HTLs) to boost the performance of optoelectronic devices is critically important. However, the fabrication of large-area high-quality SCTFs with thin thickness still remains a significant challenge due to the elusive growth mechanism of this process. In this work, the influence of three key factors on in situ growth of high-quality large-size MAPbBr3 SCTFs on HTLs is investigated. An optimal "sweet spot" is determined: low interface energy between the precursor solution and substrate, a slow heating rate, and a moderate precursor solution concentration. As a result, the as-obtained perovskite SCTFs with a thickness of 540 nm achieve a record area to thickness ratio of 1.94 × 104 mm, a record X-ray diffraction peak full width at half maximum of 0.017°, and an ultralong carrier lifetime of 1552 ns. These characteristics enable the as-obtained perovskite SCTFs to exhibit a record carrier mobility of 141 cm2 V-1 s-1 and good long-term structural stability over 360 days.
Calcium Compounds , Oxides , Titanium , Calcium Compounds/chemistry , Oxides/chemistry , Titanium/chemistry
Extensive investigation of the passivating agents has been performed to suppress the perovskite defects. However, very few attentions have been paid to rationally design the passivating agents for the balance of the carrier confinement and transfer in quasi-2D perovskites, which is essential to achieve high-performance perovskite LEDs (PeLEDs). In this work, tributylphosphine oxide (TBPO) with moderate carbon chain length is demonstrated as a decent passivator for the quasi-2D perovskites by strengthening the carrier confinement for massive radiative recombination within the perovskites, and more importantly providing efficient carrier transfer in the quasi-2D perovskites. Benefiting from these interesting optoelectronic properties of TBPO-incorporated perovskites, we achieve high-efficient blue PeLEDs with an external quantum efficiency up to 11.5% and operational stability as long as 41.1 min without any shift of the electroluminescence spectra. Consequently, this work contributes an effective approach to promote the carrier confinement and transfer for high-performance and stable blue PeLEDs.
Electron donors and acceptors in organic solar cells (OSCs) shall strike a favorable vertical phase separation that acceptors and donors have sufficient contact and gradient accumulation near the cathodes and anodes, respectively. Random mixing of donors/acceptors at surface will result in charge accumulation and severe recombination for low carrier-mobility organic materials. However, it is challenging to tune the vertical distribution in bulk-heterojunction films as they are usually made from a well-mixed donor/acceptor solution. Here, for the first time, it presents with solid evidence that the commonly used 1-chloronaphthalene (CN) additive can tune the donor/acceptor vertical distribution and establish the mechanism. Different from the previous understanding that ascribed the efficiency enhancement brought by CN to the improved molecular stacking/crystallization, it is revealed that the induced vertical distribution is the dominant factor leading to the significantly increased performance. Importantly, the vertical distribution tunability is effective in various hot nonfullerene OSC systems and creates more channels for the collection of dissociated carriers at corresponding organic/electrode interfaces, which contributes the high efficiency of 18.29%. This study of the material vertical distribution and its correlation with molecular stacking offers methods for additives selection and provides insights for the understanding and construction of high-performance OSCs.
Lead halide perovskite and organic solar cells (PSCs and OSCs) are considered as the prime candidates currently for clean energy applications due to their solution and low-temperature processibility. Nevertheless, the substantial photon loss in near-infrared (NIR) region and relatively large photovoltage deficit need to be improved to enable their uses in high-performance solar cells. To mitigate these disadvantages, low-bandgap organic bulk-heterojunction (BHJ) layer into inverted PSCs to construct facile hybrid solar cells (HSCs) is integrated. By optimizing the BHJ components, an excellent power conversion efficiency (PCE) of 23.80%, with a decent open-circuit voltage (Voc ) of 1.146 V and extended photoresponse over 950 nm for rigid HSCs is achieved. The resultant devices also exhibit superior long-term (over 1000 h) ambient- and photostability compared to those from single-component PSCs and OSCs. More importantly, a champion PCE of 21.73% and excellent mechanical durability can also be achieved in flexible HSCs, which is the highest efficiency reported for flexible solar cells to date. Taking advantage of these impressive device performances, flexible HSCs into a power source for wearable sensors to demonstrate real-time temperature monitoring are successfully integrated.
Tin-lead (Sn-Pb) perovskites have shown great potential in applications of single-junction perovskite solar cells (PSCs) and tandem devices due to outstanding photoelectrical properties and low band gaps. Currently, Sn-Pb PSCs typically have a p-i-n structure, but choices of hole transport layer (HTL) materials are very limited and there are different concerns in each of them. Eliminating the HTL is a direct and promising strategy to address the concerns, but is rarely studied. In this work, we demonstrate HTL-free and MA-free based Sn-Pb PSCs and a synergistic integration strategy of simultaneously introducing a reducing agent and in situ surface passivation. With the integration strategy, Sn-Pb perovskite films with enhanced antioxidation, reduced trap density, prolonged carrier lifetime, and improved energy-level alignment are achieved. Consequently, final HTL-free PSCs exhibit a champion power conversion efficiency (PCE) of 17.4%, which is a new record for HTL-free and MA-free Sn-Pb PSCs. Meanwhile, the integration strategy-based HTL-free device maintains excellent stability with efficiency unchanged for the first 200 h, and finally retaining 81% of the efficiency after 480 h aging in the air. This study shows the potential of achieving desirable HTL-free and MA-free Sn-Pb PSCs and offers more opportunities for tandem solar cells and other photovoltaic devices.
Considering that the periodic photonic nanostructures are commonly realized by expensive nanofabrication processes and the tunability of structure parameters is limited and complicated, we demonstrate a solution-processed upside-down molding method to fabricate photonic resonators on perovskites with a pattern geometry controllable to a certain extent. This upside-down approach not only reveals the effect of capillary force during the imprinting but also can control the waveguide layer thickness due to the inversion of the perovskite membranes.
Although inverted (p-i-n) structure perovskite solar cells (PSCs) have achieved high efficiency by commonly using fullerenes or their derivatives as electron transport layers (ETLs), the device stability and cost of fullerene materials are still of great concern. Herein, we demonstrate inorganic top ETLs simply composed from a family of metal oxides including In2O3 and its derivative of Sn:In2O3 with a gradient potential structure. For inverted PSCs, the typical film formation process of In2O3 will damage or degrade perovskite materials underneath; thus, we report a low temperature synthesis approach for obtaining In2O3 and Sn:In2O3 nanoparticles that can form effective top ETLs without any post-treatment. The one-family oxide-based top ETL features with the enhanced built-in potential, high electron extraction, and low interfacial recombination, offering a power conversion efficiency (PCE) of 20.65% in PSCs constructed from oxide-only carrier (both hole and electron) transport layers (CTLs), which is the highest efficiency in oxide-only CTL-based inverted PSCs to the best of our knowledge. Equally important, the inverted PSCs based on the Sn:In2O3/In2O3 ETL show the excellent operational stability and remain 90% of the initial value of PCE over 2000 h. Consequently, this work contributes to the robust strategy of all oxide-only CTLs in developing rigid and flexible PSCs for practical photovoltaic applications.
In this study, we demonstrate a new hybrid three-dimensional (3D) nanostructure system as an efficient hole transport layer (HTL) by a facile design of a low-temperature solution process. It is realized by integrating high-conductive chromium-doped CuGaO2 nanoplates synthesized with choline chloride (denoted as Cr/CuGaO2-CC) into ultrasmall NiOx nanoparticles. First, we propose to incorporate a Cr-doped strategy under hydrothermal synthesis conditions together with controllable intermediates and surfactants' assistance to synthesize fine-sized Cr/CuGaO2-CC nanoplates. Subsequently, these two-dimensional (2D) nanoplates serve as the expressway for improving hole transportation/extraction properties. Meanwhile, the ultrasmall-sized NiOx nanoparticles are employed to modify the surface for achieving unique surface properties. The HTL formed from the designed hybrid 3D-nanostructured system exhibits the advantages of smooth and full-covered surface, remarkable charge collection efficiency, energy level alignment between the electrode and perovskite layer, and the promotion of perovskite crystal growth. Consequently, nearly 20% of power conversion efficiency with negligible hysteresis is achieved in inverted perovskite solar cells (PSCs). This work not only demonstrates the potential applications of a 3D-nanostructured Cr/CuGaO2-CC/NiOx hybrid HTL in PSCs but also provides a fundamental insight into the design of hybrid material systems by manipulating electric behavior and morphology structure for achieving high-performance photovoltaic devices.
The long-term operational stability of perovskite light-emitting diodes (PeLEDs), especially red PeLEDs with only several hours typically, has always faced great challenges. Stable ß-CsPbI3 nanocrystals (NCs) are demonstrated for highly efficient and stable red-emitting PeLEDs through incorporation of poly(maleic anhydride-alt-1-octadecene) (PMA) in synthesizing the NCs. The PMA can chemically interact with PbI2 in the precursors via the coupling effect between O groups in PMA and Pb2+ to favor crystallization of stable ß-CsPbI3 NCs. Meanwhile, the cross-linked PMA significantly reduces the PbCs anti-site defect on the surface of the ß-CsPbI3 NCs. Benefiting from the improved crystal phase quality, the photoluminescence quantum yield for ß-CsPbI3 NCs films remarkably increases from 34% to 89%. The corresponding red-emitting PeLEDs achieves a high external quantum efficiency of 17.8% and superior operational stability with the lifetime, the time to half the initial electroluminescence intensity (T50 ) reaching 317 h at a constant current density of 30 mA cm-2 .
